Treatment of textile materials



Patented Nov. 2, 1937 PATENT v OFFICE I TREATMENT OF TEXTILE MATERIALS Henry Dreyfus, London, England No Drawing. Application August 24, 1935, Serial No. 37,781. In Great Britain August so, 1934 s Claims. (01. 91-68) This invention relates to improvements in the treatment of textile materials, and is more particularly concerned with fixing therein insoluble substances and particularly insoluble metal oxides or compounds. The invention is particularly valuable in the treatment of artificial textile materials, for example those of cellulosic character or those made of cellulose acetate or other organic derivatives of cellulose.

10 Recently considerable research has been carried out with a view to decreasing or modifying the normal high lustre of artificial silk materials by incorporating therein white opaque compounds, generally insoluble metal oxides or other metal compounds. Proposals to this end have included spinning the artificial silk from solutions containing in suspension the finely divided metal oxides or compounds. Such processes, while yielding artificial silk of dull lustre, necessitate providing stocks of artificial silk both of dull lustre and ordinary bright lustre. Other processes effect a dulling of the lustre of artificial silk after its formation. Such processes involve the successive application of two or more soluble reagents to the materials with resultant precipitation in or on the materials of insoluble metal oxides or compounds While these processes have the advantage that stocks of artificial silk of normal bright lustre can readily be converted into materials of dull lustre,- nevertheless the fastness of the delustring agent upon the material frequently leaves something to be desired. In particular in scouring and in other normal finishing processes, and in domestic washing or other laundering operations, the delustring agent or some of it is liable to be removed with consequent change in the appearance of the artificial silk.

Similarly, for certain purposes it is desirable to load artificial silk not with the object of dulling its lustre but with the object of imparting to it a fuller handle and/or with the object of increasing its safe ironing point or of modifying the dyeing properties. Thus, for instance, artificial silk made of cellulose derivatives may be loaded with tin 45 compounds, for example by treatment with a stannic chloride solution followed by fixation with phosphate and/or silicate solution. It is desirable in order to obtain any'substantial loading of the material to apply the tin salt or other solution containing the loading metal radicle under conditions such that the cellulose derivative is in a swollen condition. For example the material may be treated with a swelling agent. or a swelling agent may be included in the stannic chloride or similar loading bath, or alternatively the stannlc chloride or similar loading agent may be applied under such conditions of concentration and temperature-that it constitutes a swelling agent for the material under treatment.- Instead of loading with stannic chloride, phosphate and/or 5 silicate, other insoluble loading agentsmay be formed in or on the materials, for example phosphates, silicates, borates and the like of the alkaline earth metals, for instance calcium, barium, strontium or of lead or other heavy metals. Some 30 of these metal compounds, particularly the alkaline earth compounds, have the effect of dlminishing the lustre of the materlal in addition to imparting a substantial loading. The silicate, phosphate or like fixing agent, though preferably applied subsequent to the stannicchloride or other metal loading solution, may be applied prior thereto. Where materials containing saponifiable organic esters of cellulose are being treated, the silicate, phosphate or other fixing agent, whether 20 applied prior to or subsequent to the metallic loading solution, may effect a saponification of the cellulose ester. In such loading processes,

' again the fastness in the material of the loading compound may sometimes with advantage be 2i improved. p

In a similar manner insoluble coloured pigments may be formed in or on the material for the purpose of imparting colourations which are faster to light than are theusual dyeings produced 30 with organic dyestufis. Any lack of fastness to scouring, washing or similar treatments obviously counterbalances the increased fastness to lightof the colouring agent. v

It is the object of the present invention to 35. improve the fastness to scouring, washing and similar treatments of insoluble substances fixed in or on textile materials. According to the present invention the fastness of such insoluble substances in or on the textile materials is improved by applying to the textiles a film-forming substance insoluble or substantially insoluble in water or the. usual scouring-liquids. Preferably such film forming substance is applied in very small amounts so that the properties of the materials as textiles are in no way impaired. Thus, the film-. forming materials may be applied to the textiles in very low proportions, and particularly in amounts 'of under 5% by weight of the textile under treatment. Proportions as low as 3, 2, and- 1% or under may be'used with advantage and still improve the fastness of the insoluble compounds fixed in or on the textile materials.

A further important feature of the present invention consists in applying the film-forming substances from dilute solutions or dispersions so thatlittie or no sticking of the individual filaments, fibres or yarns of the'textiles takes place For instance with this object in view it is desirable to apply the film-forming substances in solutions or dispersions of a concentration under 5% and preferably as low as 2 or 1% or less.

The difficulty as to the fastness to scouring and similar agencies of insolubleloading, delustring and similar agents arises more particularly with artificial textile materials. Cellulose derivative materials are sepecially improved by the process of the present invention. As is well known, these materials are relatively impervious to aqueous media and therefore difllculties arise in the loading, delustring and similar treatments of these materials wherein the reagents designed to form in the materials the delustring, loading and similar agents are applied in aqueous media. Usually it is necessary to swell the cellulose derivative duringthe treatment, and especially during the treatment with a soluble metallic comfpound. In sufi'icient penetration of the materials by the aqueous reagents may well be responsible for lack of fastness of the insoluble compound formed on the materials. Probably the smooth character of artificial silk materials also tends to render the loading, delustring or similar agent less fast to scouring-washing and like treatments.

- The present invention embraces quite broadly the application of any film-forming substance which is insoluble or substantially insoluble in water and in the ordinary scouring and washing baths. A wide variety of film-forming substances is available for the purpose, for example polymerized unsaturated organic compounds generally, for instance polymerized vinyl acetate, polymerized vinyl chloracetate and other polymerized vinyl esters, polyvinyl ethers,polystyreneandsimilar polymerized unsaturated hydrocarbons, polymerized unsaturated aliphatic aldehydes, polymerized esters of unsaturated aliphatic acids, for instance, polymerized acrylic ester and polymerized methacrylie ester; various film-forming condensation products, including urea formaldehyde condensation products, phenol aldehyde condensation products and mixed phenol urea aldehyde condensation products, condensation productsof polyalcohols with polybasic acids, e. g. the socalled alkyd resins, made, for example, by the condensation of glycerin with phthalic anhydrlde, and modified alkyd resins, made by reaction between an alkyd resin and an oil or a higher fatty acid. Such polymerization and/or condensation products may be applied in the fully polymerized and/or condensed form, provided they are soluble or dispersible in organic liquids or in aqueous liquids, or they may be applied in apartially polymerized and/or condensed form, with or without subsequent further polymerization or condensation upon the material. If desired the reagents in the unpolymerized or uncondensed form may be applied to the materials and the .whole of the polymerization and/or condensation desired effected upon the materials. Generally it is undesirable to employ in such polymerization and/or condensation processes carried out on the materials, temperatures in excess of about 180 C. Preferably temperatures below 150 C. are employed.

Other film-forming bodies which are useful for the purpose of the present invention include cellulose and cellulose derivatives, for example nitrocellulose, cellulose acetate, formate, propionate,

'butyrate and benzoate, methyl-, ethylor benzylcelluloses' or other cellulose esters or cellulose ethers or mixed esters, mixed ethers or mixed ether-esters, for instance oxyethyl cellulose acetate; and solutions of cellulose including viscose and cuprammonium cellulose. The ordinary alkali metal cellulose xanthate solution may be employed or any other soluble or dispersible cellulose xanthate, for example, ammonium cellulose xanthate or a cellulose xanthate of an organic amino base or magnesium cellulose xanthate. Chlorinated rubber is also suitable as a, film-forming substance for the purpose of the present invention. Rubber itself is suitable for increasing the fastness of the loading, delustring or other compounds but has the disadvantage that it tends to oxidize in theair. especially in the very thin films in which it is applied according' to the present invention. Balata, gutta percha and like bodies have similar properties.

As previously indicated, the invention particularly contemplates the application of very small proportions of film-forming substances to the textile materials, and to achieve this low concentrations of the film-forming substances in suitable solvent or dispersion media are especially valuable. The invention more particularly contemplates the application of the film-forming substance to the textile material already loaded with the loading, delustring or other agent.

If desired, however, the film-forming substance may, where feasible, be included in" one or other of the reagents for forming the loading, delustring or other compound upon the material. Latex, for example, may be included in a neutral or alkaline reagent; Similar remarks apply to the alkali metal cellulose xanthates, ammonium and amine cellulose xanthates and magnesium cellulose xanthate. Thus, for instance, where an insoluble borate, silicate or phosphate is being formed upon the material, such a xanthate or other film-forming substance, stable, in the presence of alkali or neutral media, may be dissolved or dispersed in a neutral or alkaline aqueous solution of an alkali metal, silicate, phosphate or borate used for fixing upon the material the loading or delustring metal, for example tin, barium, strontium, calcium and magnesium. The

' film-forming substance may be included in such a fixing solution, whether the fixing agent be ap plied before or after the metal salt solution. Further, where feasible a film-forming substance -may be dissolved or dispersed in the solution of the insoluble substance upon the materials, the

medium in which it is applied will generally be an aqueous medium. Where it is applied subsequent to the formation. on the material of the loading, delustring or other agent, it may be ap plied either in an aqueous or in an organic me-' dium. Generally the film-forming substances are insoluble in water, so that for application in aqueous media they must be dispersed. However, the film-forming substances may be present in aqueous solution in a soluble form and may beconverted upon the material into an insoluble form. Such is the case with viscose and cuprammonium-cellulose and various unpolymerised or uncondensed reagents or partially polymerized and/or condensed substances to be subsequently polymerized or condensed or further polymerized or condensed on the textile material. For instance, a viscose solution may be applied to a loaded cellulose acetate fabric and may be subsequently steamed or treated with a solution of ammonium acetate, acetic acid, sulphuric acid or other precipitant for the xanthate.

Cellulose acetate and similar cellulose esters,

ethers, or ether-esters, the polyvinyl esters, ethers or other compounds, the polymerized acrylic esters and similar polymerized unsaturated esters, and the polymerized aldehydes are most conveniently applied from an organic solvent, for example methyl .or ethyl alcohol or other alcohol; acetone, methyl ethyl ketone or other ketone;

glycols, glycerine glycol ethers, glycol esters and glycol ether-esters, methyl formate, ethyl formate;

for preventing damage to textiles consisting of I cellulose derivatives during theapplication of the film-forming substance.

Generally the medium in which the film-forming substance is applied to the textile material cellulose derivatives.

' should have no substantial solvent action upon the textile material. This isparticularly important with textile materials made of or containi However, some solvent actionof the medium in which the film-forming substance is applied upon the textile material under treatment is advantageous in that it appears to secure a better anchoring of the film-forming substance to the textile material. If desired the film-forming substance may be of the same chemical character as the textile material under treatment. For example a cellulose derivative fabric may be coated with a thin film of cellulose derivative.

It is desirable that the film-forming cellulose derivative shall have diflerent solubility properties from those of the cellulose derivative present in the textile material. If suitable precautions are taken, however, the film-forming substance may be identical or substantially identical with the substance of the textile. For instance a loaded or delustred cellulose acetate fabric may have a cellulose acetate applied thereto. The filmforming cellulose acetate may be such as will dissolve in a 30-40% aqueous solution of .acetone, acetic acid or dioxane at ordinary or high temperatures; Having regard to the low concentra= tions in which the film-forming substances are preferably applied according to the present invention, this presents no dimculty. A cellulose acetate can readily be prepared which is soluble to the required extent in such an aqueoussoivent, even at ordinary temperatures, by arranging the conditions of acetylation, including pre-treatmerit, acetylation proper and ripening, so as to yield a cellulose acetate of comparatively low viscosity. A suitable cellulose acetate may, for example, be dissolved to a concentration of about 1% in a 20-35% aqueous solution of acetic acid at IO- C. and applied in this form to a cellulose acetate fabric. Preferably after the application of the solution the fabric is rapidly cooled. Evaporation of the solvent may be eifected at low or relatively low temperatures. Instead of evaporating the solvent, the latter may be so chosen that it is a solvent for the film-forming substance while hot and a non-solvent when cold, so that a hot solution may be applied to the textile and the film-forming substance precipitated thereon by mere cooling.-

The film-forming substance may be applied to A the textile materials by any suitable method, for example mechanical impregnation, bath treatments, spraying or the like. impregnation followed by a squeezing of the fabric so that it re-' tains a predetermined amount ofthe film-forming solution or dispersion is particularly useful for the purpose of the present invention, since it enables a very uniform application of the filmforming substance in the desired small quantity to be achieved very readily. A loaded or delustredtextile fabric may, for example. be passed through a solution or dispersion of the film-forming substance in a bath or in a padding mangle and the fabric squeezed so as to retain 50,. or

% of its own weight of the solution or dispersion, and the fabric may thereafter be dried or otherwise treated to fix the'film-forming substance thereon. A very convenient procedure consists in applying tothe fabric a solution of ,the film-forming substance in a concentration of 1A to 1 or 2% and subsequently expressing the film-forming solution so that the fabric contains a quantity of.50-100% of its own weight of the solution.

As previously indicated, the process of the invention is of the greatest importance in relation toimproving the fastness of loading. delustring or other insoluble substance upon materials made r of or containing cellulose acetate or other cellulose derivatives. In this connection reference is made to the delustring or loading processes of U. S. applications S. Nos. 30,944 and 30,945 filed July 11, 1935 and applications S. Nos, 37,779 and. 37,780 filed Aug. 24, 1935. i

The following examples are given in order to illustrate the invention, but it is to be understood that they do not limit it in any way:-

Example 1 A fabric of natural silk yarn is steeped in a stannic chloride solution of 40-50 Tw. for half an hour at a temperature of 40-50 C., thoroughly rinsed and then steeped in a solution of disodium phosphate of 4-6" Tw. for halfan hour at 40-45 C. The fabric is rinsed, washed in soap solution, rinsed again and then dried.

The dry, loaded fabric is then treated with a 1% solution of cellulose acetate in acetone, passed through nipping rollers to express the solution so that the fabric retains about its own weight of the solution, and dried.

The film of' cellulose acetate thus formed on the loaded fabric appreciably reduces the loss in weight occasioned by repeated scouring without changing the appearance of the fabric.

Example 2 A fabric of cellulose acetate yarn is steeped for 1 hourat about 20? C. in a loading bath containing about 280 grams of stannic chloride (SnChfiHsO) and 243 grams of ammonium thiocyanate per litre. The fabric is removed from the bath, drained well and washed first in two baths of cold water and then in two baths cf water at 45 C. until quite free from soluble salts.

to the dry fabric in the form of a 135% solution in this solvent, the fabric being passed through nipping rollers to express the solution so that the fabric retains about its own weight of the solution, after which the fabric is dried.

The film of polymerized vinyl acetate thus formed on the fabric appreciably reduces the loss in weight occasioned by repeated scouring without altering the appearance or dyeing properties of the fabric.

Example 3 A fabric of cellulose acetate yarn is treated with a fairly concentrated solution of sodium aluminate, centrifuged and then, while still moist, stretched out or hung in a chamber in which it is exposed at 50-70 C. to the moist carbon dioxide. The fabric is then washed until free from sodium carbonate and dried.

The fabric loaded with aluminium hydroxide thus obtained is treated with a solution of viacose containing 2% of cellulose for half a minute at 26 C. and squeezed so that it retains about its own weight of solution. The fabric is then placed in a precipitating bath, consisting of a aqueous solution of aluminium acetate. for 2 minutes at 26 C. The fabric is then thoroughly washed and dried.

The fabric thus obtained does not suffer substantial loss in weight even after repeated scour- 8.

What I claim and Patent is:-

1. In a process for the manufacture of textile materials impregnated with an insoluble metal compound, the step which comprises improving the fastness of said metal compound without substantially impairing the properties of the textile'materials by applying to the textile materials impregnated therewith a solution in a volatile desire to secure by Letters organic solvent of a substance which forms a film on the materials which is substantially'insoluble in aqueous scouring liquids, the film forming-substance being applied in a quantity less than 5% of the weight of the textile materials treated.

2. In a proces for the manufacture of textile materials impregnated with an insoluble metalcompound, the step which comprises improving the fastness of said metal compound without substantially impairing the properties of the textile materials by applying to the textile materials p nated therewith a solution in a volatile organic solvent of a substance which forms a film on the materials which is substantially insoluble in aqueous scouring liquids, the filmforming substance being applied in a quantity equal to $5 to 2% of the weightof the textile 'materials treated.

the fastness of said metal compound without.

substantially impairing the properties of the textile materials by applying to the textile materials impregnated therewith a solution of less than 5% concentration in a volatile organic solvent of a substance which forms a film on the materials which is substantially insoluble in aqueous scourimpregnated therewith a solution of it to 2% concentration in a volatile organic solventof a substance which forms a film on the materials which is substantially insoluble in aqueous scouring liquids, the fllm-fomring substance being applied in a quantity equal to to 2% of the weight of the textile materials treated.

5. In a process for the manufacture of textile materials impregnated with an insoluble metal compound, the step which comprises improving the fastness of said metal compound without sub stantially impairing the properties of the textile materials by applying to the textile materials impregnated therewith a solution of cellulose acetate in a volatile organic solvent so as to form a film of cellulose acetate on the materials which is substantially insoluble in aqueous scouring liquids, the film-forming substance being applied in quantity less than 5% of the weight of the textile materials treated.

6. In a process for the manufacture of textile materials impregnated with an insoluble metal compound, the step which comprises improving the fastness of said metal compound without substantially impairing the properties of the textile materials by applying to the textile materials impregnated therewith a $6 to 2% solution of cellulose acetate in a volatile organic solvent so as to form a film of cellulose acetate on the materials which is substantially insoluble in aqueous scouring liquids, the quantity of cellulose acetate applied being equal to A to'2% of the weight of the textile materials treated.

I 7. In a process for the manufacture of textile -materials impregnated with an insoluble metal compound, the step which comprises improving the fastness of said metal compound without substantially impairing the properties of the textile materials by applying to the textile materials weight of the materials treated.

8. In a process for the manufacture of textile materials impregnated with an insoluble metal compound, the step which comprises improving the fastness of said metal compound without substantially impairing the properties of the textile materials by applying to the textile materials impregnated therewith a it to 2% solution in a volatile organic solvent of vinyl acetate so as to form a film of vinyl acetate on the materials which is substantially insoluble in aqueous scouring liquids, the vinyl acetate being applied in a quantity equal to V to 2% of the weight of the materials treated.

,- HENRY DREYFUSV 

